The coordination chemistry of two symmetric double-armed oxa­diazole-bridged organic ligands with copper salts

Two new symmetric double-armed oxa­diazole-bridged ligands, 4-methyl-{5-[5-methyl-2-(pyridin-3-yl­carbon­yl­oxy)­phen­yl]-1,3,4-oxa­diazol-2-yl}phenyl pyridine-3-carboxyl­ate (L1) and 4-methyl-{5-[5-methyl-2-(pyridin-4-yl­carbon­yl­oxy)­phen­yl]-1,3,4-oxa­diazol-2-yl}phenyl pyridine-4-carboxyl­ate (L2), were prepared by the reaction of 2,5-bis­(2-hy­droxy-5-methyl­phen­yl)-1,3,4-oxa­diazole with nicotinoyl chloride and iso­nicotinoyl chloride, respectively. Ligand L1 can be used as an organic clip to bind Cu^II cations and generate a mol­ecular complex, bis­(4-methyl-{5-[5-methyl-2-(pyridin-3-yl­carbon­yl­oxy)phen­yl]-1,3,4-oxa­diazol-2-yl}phenyl pyridine-3-carboxyl­ate)bis­(perchlorato)­copper(II), [Cu(ClO₄)₂(C₂₈H₂₀N₄O₅)₂], (I). In com­pound (I), the Cu^II cation is located on an inversion centre and is hexa­coordinated in a distorted octa­hedral geometry, with the pyridine N atoms of two L1 ligands in the equatorial positions and two weakly coordinating perchlorate counter-ions in the axial positions. The two arms of the L1 ligands bend inward and converge at the Cu^II coordination point to give rise to a spirometallocycle. Ligand L2 binds Cu^I cations to generate a supra­molecule, diaceto­nitrile­di-[mu]₃-iodido-di-[mu]₂-iodido-bis­(4-methyl-{5-[5-methyl-2-(pyridin-4-yl­carbon­yl­oxy)­phen­yl]-1,3,4-oxa­diazol-2-yl}phenyl pyridine-4-carboxyl­ate)tetracopper(I), [Cu₄I₄(CH₃CN)₂(C₂₈H₂₀N₄O₅)₂], (II). The asymmetric unit of (II) indicates that it contains two Cu^I atoms, one L2 ligand, one aceto­nitrile ligand and two iodide ligands. Both of the Cu^I atoms are four-coordinated in an approximately tetra­hedral environment. The molecule is centrosymmetric and the four I atoms and four Cu^I atoms form a rope-ladder-type [Cu₄I₄] unit. Discrete units are linked into one-dimensional chains through [pi]-[pi] inter­actions.

S1. Comment

In recent years, research into the design and synthesis of metal–organic frameworks (MOFs) has become an active area in the fields of crystal engineering and supramolecular chemistry, not only because of their tremendous potential applications in gas storage (Thallapally et al., 2008; Rowsell & Yaghi, 2005), selective absorption (Dong et al., 2007; Xiao et al., 2011), catalysis (Wu & Lin, 2007), luminescent materials (Chen et al., 2012) and heterogeneous catalysis (Dang et al., 2010), but also because of their intriguing variety of architectures and topologies (Biradha et al., 2006). Numerous supramolecular networks based on metal-containing molecular building blocks linked through C—H···π (Munshi et al., 2004) and π–π (Khavasi & Fard, 2010) interactions have recently been shown to have a dramatic effect on molecular packing features.

Oxadiazole-bridged compounds are very important organic ligands in organometallic chemistry. The bridging five-membered oxadiazole rings ensure that the geometries of these ligands are not linear. The specific geometry of this type of ligand may result in coordination polymers with novel network patterns not achievable by other rigid linear organic ligands. They are widely used in the construction of organometallic complexes (Fang et al., 2011; Du et al., 2011). During the past decade, the design and construction of both rigid and flexible organic ligands bridged by 1,3,4-oxadiazole have been pursued, due to their diversity in coordination chemistry and model applications as functional materials (Jabbour et al., 2002; Hughes & Bryce, 2005; Du et al., 2010). As a result of the bent shape of the oxadiazole-containing ligands and their use in electroluminescent and sensitizing applications, our group has been exploring coordination chemistry based on oxadiazole-bridged bent organic ligands (Dong et al., 2003). It is well known that N-donor ligands, such as those containing pyridyl groups, are good condidates for the assembly of versatile structures (Fujita et al., 2007). As part of our continuing study of coordination compounds with oxadiazole-bridged ligands, we incorporated pyridyl groups into the ligands 4-methyl-{5-[5-methyl-2-(pyridin-3-ylcarbonyloxy)phenyl]-1,3,4-oxadiazol-2-yl}phenyl pyridine-3-carboxylate (L1) and 4-methyl-{5-[5-methyl-2-(pyridin-4-ylcarbonyloxy)phenyl]-1,3,4-oxadiazol-2-yl}phenyl pyridine-4-carboxylate (L2), and two new complexes, [Cu(ClO₄)₂(L1)₂], (I), and [Cu₄I₄(L2)₂(CH₃CN)₂], (II), were obtained.

Complex (I) is generated from the assembly of L1 and copper perchlorate (Fig. 1; relevant bond distances and angles are provided in Table 1) and crystallizes in the triclinic space group P1. Our group reported a study of the copper perchlorate coordination chemistry of 2,5-bis[2-(4-pyridylcarbonyl)phenyl]-1,3,4-oxadiazole [···2-(4-pyridylcarbonyloxy)phenyl···?] (Dong et al., 2006). In that study, the Cu^II centre in compound (III) (see scheme) lies in a six-coordinate 4+2 pseudo-octahedral geometry, defined by four pyridyl N-donors from two ligands and two O atoms from two weakly coordinated ClO₄^- anions. In complex (I), the Cu^II centre shows a coordination environment similar to that of (III). The Cu^II centre in (I) is located on an inversion centre at (1,0,1) and is coordinated in a distorted octahedral geometry by the pyridyl N atoms of two L1 ligands in the equatorial positions and by two weakly coordinating perchlorate counter-ions in the apical positions. The torsion angles for the two benzene rings are -25.6 (6) (C7—C12—C14—N2) and 28.1 (6)° (N3—C15—C16—C21). The corresponding dihedral angles formed by the planes of the three rings are 26.5 (1) (C7–C12 and O1/N2–N3/C1–C15), 29.0 (1) (C16–C21 and O1/N2/N3/C14–C15) and 32.3 (1)° (C7–C12 and C16–C21). The dihedral angle between the two pyridine rings is 76.9 (1)° (N1-plane and N4-plane).

In (I), the two flexible pyridine-3-carboxylate arms on each L1 ligand bend inward, and the Cu^II centre links two ligands into a spirometallocycle consisting of two 19-membered rings. The two coordinated ClO₄^- counter-ions are located on both sides of the ring plane. Two ClO₄^- anions display anion···π interactions through atoms O7 and O7ⁱ [symmetry code: (i) -x + 2, -y, -z + 2] to the N2ⁱ/N3ⁱ and N2/N3 oxadiazole rings, respectively, of the two L1 ligands (Fig. 2). The centroid···O distances are both 2.95 (3) Å, shorter than the corresponding distance of 3.26 (1) Å reported in the literature (Mastropietro et al., 2012). This type of noncovalent supramolecular interaction involving anions and aromatic heterocyclic nitrogen systems is a subject of increasing interest from both theoretical and experimental points of view because of their relevance in chemistry and structral biology, and also because of their potential role in the design of anion receptors (Mascal et al., 2002; Ahuja & Samuelson, 2003).

Compound (II) is generated from the assembly of L2 and copper iodide (Fig. 3; relevant bond distances are provided in Table 2), and it crystallizes in the triclinic space group P1 as well. Crystallographic analysis of (II) indicates that it contains two Cu^I cations, one L2 ligand, one acetonitrile ligand and two iodide ligands. There are two types of Cu^I centre and they are located on an inversion centre at (1/2,1/2,0). Atoms Cu1 and Cu2 are both four-coordinate in an appoximately tetrahedral environment. Atom Cu1 lies in a {CuNI₃} coordination environment consisting of one pyridyl N-donor and three iodide anions. Atom Cu2 lies in a {CuN₂I₂} coordination environment consisting of one pyridyl N-donor from L2, one acetonitrile N-donor and two iodide anions. The two benzene rings and the central oxadiazole ring are almost coplanar. The corresponding dihedral angles formed by the planes of the three rings are 7.5 (2) (C16–C22 and O1/N2–N3/C14–C15), 1.0 (1) (C7–C13 and O1/N2–N3/C14–C15) and 7.8 (1)° (C7–C13 and C16–C22). The dihedral angle between the two pyridyl rings is 72.3 (2)° (N1-plane and N4-plane). The two pyridyl N atoms of the ligand chelate to two Cu^I cations alternately (Yang et al., 2007; Addison & Rao, 1984). In addition, four I atoms and four Cu^I cations form a rope-ladder type [Cu₄I₄] unit extending along the (021) plane (Fig. 5). One [Cu₄I₄] unit and two ligands form two malposed 23-member bimetallic rings in a head-to-head fashion. Two acetonitrile molecules, which act as terminal functional groups, prevent the rope ladder from extending.

In the solid state, complex (II) assembles into a one-dimensional structure through weak π–π interactions (Fig. 4), which occur between pairs of oxadiazole rings and phenyl rings. The centroid-to-centroid distance for these π–π interactions is 3.5 (6) Å for pairs of rings involving atoms O1ⁱ/N2ⁱ–N3ⁱ/C14ⁱ–C15ⁱ [symmetry code: (i) -x + 1, -y + 1, -z] and atoms C7–C10/C12–C13, which is close to the corresponding distance of 3.49 Å reported in the literature (Choudhury et al., 2008). The perpendicular distance is 3.3 (2) Å.

In summary, through the assembly of similar ligands with copper salts, two types of compound have been obtained. Compound (I) is a discrete metal complex with an `8'-shaped structure, while (II) has a different structure of a [Cu₄I₄] unit; one [Cu₄I₄] unit and two ligands form two bimetallic rings in a head-to-head fashion. It is clearly demonstrated that these types of ligand can act as distinct building blocks, leading to different complexes. We are currently extending this research by preparing new symmetric and nonsymmetric oxadiazole-containing ligands of this type containing different coordination functional groups and having different orientations of the terminal coordination sites. We anticipate that such organic ligands will result in a variety of new coordination polymers with novel polymeric patterns and interesting chemical and physical properties.

Related literature

For related literature, see: Addison & Rao (1984); Ahuja & Samuelson (2003); Biradha et al. (2006); Chen et al. (2012); Choudhury et al. (2008); Dang et al. (2010); Dong et al. (2003, 2006, 2007); Du et al. (2010, 2011); Fang et al. (2011); Fujita et al. (2007); Hughes & Bryce (2005); Jabbour et al. (2002); Khavasi & Fard (2010); Mascal et al. (2002); Mastropietro et al. (2012); Munshi et al. (2004); Rowsell & Yaghi (2005); Thallapally et al. (2008); Wu & Lin (2007); Xiao et al. (2011); Yang et al. (2007).

S2. Experimental

For the preparation of L1, 2,5-bis(2-hydroxy-5-methylphenyl)-1,3,4-oxadiazole (1.41 g, 5.00 mmol), nicotinoyl chloride (1.96 g, 11.00 mmol) and triethylamine (2.00 ml, 15.00 mmol) were combined in dry tetrahydrofuran (50 ml) with stirring at ambient temperature for 6 h. The reaction was monitored by thin-layer chromatography (TLC). After removal of the solvent under vacuum, the residue was purified by silica-gel column chromatography using dichloromethane and tetrahydrofuran (1:1 v/v) as eluent to afford L1 as a white solid (yield 2.20 g, 4.50 mmol, 89.52%). Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, 298 K, TMS, δ, p.p.m.): 9.48 (t, 2H, –C₅H₄N), 8.85 (d, 2H, –C₅H₄N), 8.50 (d, 2H, –C₅H₄N), 7.65 (s, 2H, –C₆H₄), 7.45 (d, 2H, –C₆H₄), 7.35 (d, 2H, –C₆H₄), 7.23 (d, 2H, –C₆H₄), 2.26 (s, 6H, –CH₃); ¹³C NMR (150 MHz, CDCl₃, δ, p.p.m.): 164.09, 161.60, 153.93, 151.57, 146.04, 137.97, 136.83, 133.61, 129.54, 125.52, 123.82, 123.53, 116.74, 20.74; IR (KBr pellet, ν, cm^-1): 3420 (m), 2930 (m), 1740 (vs), 1635 (m), 1592 (m), 1510 (m), 1419 (m), 1273 (vs), 1207 (s), 1084 (s), 1020 (s), 875 (m), 727 (m). Elemental analysis, calculated for C₂₈H₂₀N₄O₅: C 68.29, H 4.09, N 11.38%; found: C 68.21, H 4.13, N 11.33%.

For the preparation of L2, 2,5-bis(2-hydroxy-5-methylphenyl)-1,3,4-oxadiazole (1.41 g, 5.00 mmol), isonicotinoyl chloride (1.96 g, 11.00 mmol) and triethylamine (2.00 ml, 15.00 mmol) were combined in dry tetrahydrofuran (50 ml) with stirring at ambient temperature for 6 h. The reaction was monitored by TLC. After removal of the solvent under vacuum, the residue was purified by silica-gel column chromatography using dichloromethane and tetrahydrofuran (1:1 v/v) as eluent to afford L2 as a white solid (yield 2.00 g, 4.50 mmol, 81.53%). Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, 298 K, TMS, δ, p.p.m.): 8.87 (s, 4H, –C₅H₄N), 8.07 (d, 4H, –C₅H₄N), 7.63 (s, 2H, –C₆H₃), 7.39 (s, 2H, –C₆H₃), 7.23 (d, 2H, –C₆H₃), 2.25 (s, 6H, –CH₃); ¹³C NMR (150 MHz, CDCl₃, δ, p.p.m.): 164.02, 161.54, 150.76, 145.97, 137.01, 136.70, 133.71, 129.53, 123.66, 123.47, 116.55, 20.66; IR (KBr pellet, ν, cm^-1): 3445 (m), 2927 (m), 1749 (vs), 1635 (m), 1542 (m), 1509 (m), 1293 (vs), 1274 (vs), 1231 (m), 1101 (m), 1062 (m), 874 (m), 726 (m), 749 (s), 694 (s). Elemental analysis, calculated for C₂₈H₂₀N₄O₅: C 68.29, H 4.09, N 11.38%; found: C 68.19, H 4.16, N 11.36%.

For the preparation of complex (I), a solution of Cu(ClO₄)₂.6H₂O (11.11 mg, 0.030 mmol) in CH₃OH and CH₃CH₂OH (1:1 v/v, 8 ml) was layered onto a solution of L1 (14.82 mg, 0.030 mmol) in CH₂Cl₂ (8 ml). The system was left for about one week at room temperature and purple crystals of (I) were obtained (yield 18.71 mg, 75.32%). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3420 (m), 2930 (m), 1740 (vs), 1635 (m), 1592 (m), 1510 (m), 1419 (m), 1273 (vs), 1207 (s), 1084 (s), 1020 (s), 875 (m), 727 (m).

For the preparation of complex (II), a solution of CuI (5.73 mg, 0.030 mmol) in CH₃CN (8 ml) was layered on to a solution of L2 (14.84 mg, 0.030 mmol) in tetrahydrofuran (8 ml). The system was left for about one week at room temperature and yellow crystals of (II) were obtained (yield 10.82 mg, 79.21%). Spectroscopic analysis: IR (KBr pellet, ν, cm^-1): 3445 (m), 2927 (m), 1749 (vs), 1635 (m), 1542 (m), 1509 (m), 1293 (vs), 1274 (vs), 1231 (m), 1101 (m), 1062 (m), 874 (m), 726 (m), 749 (s), 694 (s).

S3. Refinement

For complex (I), atoms C1, C2 and C3 were disordered over two orientations, with refined site-occupancy factors of 0.30 (4) and 0.70 (4), and the C3—C4 and C3'—C4 bonds were restrained to be the same within a standard deviation of 0.01 Å. The C2—C3 and C2'—C3' bonds were also restrained to be the same within a standard deviation of 0.01 Å. In total, two restraints were used in modelling the disorder. H atoms attached to C atoms were placed in geometrically idealized positions and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and with C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

For complex (II), H atoms attached to C atoms were placed in geometrically idealized positions and refined using a riding model, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C) for aromatic H atoms, and C—H = 0.96 Å and U_iso(H) = 1.5U_eq(C) for methyl H atoms.

Computing details

For both compounds, data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008), POV-RAY (Cason, 2003) and DIAMOND (Brandenburg, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x + 2, -y, -z + 2.]
	Fig. 2. A view of symmetric unit of (I), showing the atom-numbering scheme. The anion···π interactions between the perchlorate anion and the two L1 ligands are shown as dashed lines. [Symmetry code: (i) -x + 2, -y, -z + 2.]
	Fig. 3. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x + 1, -y + 1, -z.]
	Fig. 4. The packing of (II), showing the one-dimensional chains driven by π–π interactions (dashed lines).
	Fig. 5. The [Cu4I4] unit in (II), extending along the (021) plane. [Symmetry code: (i) -x + 1, -y + 1, -z.]

(I) Bis(4-methyl-{5-[5-methyl-2-(pyridin-3-ylcarbonyloxy)phenyl]-1,3,4-oxadiazol-2-yl}phenyl pyridine-3-carboxylate)bis(perchlorato)copper(II)

Crystal data

[Cu(ClO4)2(C28H20N4O5)2]	Z = 1
Mr = 1247.40	F(000) = 639
Triclinic, P1	Dx = 1.485 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.342 (8) Å	Cell parameters from 1591 reflections
b = 10.408 (8) Å	θ = 2.3–22.2°
c = 15.633 (12) Å	µ = 0.57 mm^−1
α = 72.226 (11)°	T = 298 K
β = 82.736 (12)°	Block, purple
γ = 60.549 (9)°	0.21 × 0.11 × 0.08 mm
V = 1394.7 (18) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	5104 independent reflections
Radiation source: fine-focus sealed tube	3514 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.026
ϕ and ω scans	θmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −12→12
Tmin = 0.890, Tmax = 0.956	k = −12→11
7366 measured reflections	l = −12→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.155	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0726P)^2 + 0.2788P] where P = (Fo^2 + 2Fc^2)/3
5104 reflections	(Δ/σ)max = 0.001
415 parameters	Δρmax = 0.49 e Å^−3
2 restraints	Δρmin = −0.36 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
C4	0.6373 (4)	0.0343 (4)	0.8700 (3)	0.0511 (10)
C5	0.7758 (4)	−0.0069 (4)	0.9000 (2)	0.0456 (9)
H5	0.8576	−0.0916	0.8871	0.055*
C6	0.6158 (4)	−0.0464 (5)	0.8141 (3)	0.0551 (10)
C7	0.7395 (4)	−0.2706 (4)	0.7659 (3)	0.0486 (9)
C8	0.6761 (5)	−0.3652 (5)	0.7851 (3)	0.0642 (12)
H8	0.6178	−0.3691	0.8353	0.077*
C9	0.7001 (5)	−0.4551 (5)	0.7285 (3)	0.0676 (12)
H9	0.6582	−0.5200	0.7419	0.081*
C10	0.7843 (4)	−0.4501 (5)	0.6535 (3)	0.0584 (11)
C11	0.8434 (4)	−0.3520 (5)	0.6353 (3)	0.0544 (10)
H11	0.8989	−0.3462	0.5840	0.065*
C12	0.8239 (4)	−0.2612 (4)	0.6900 (3)	0.0474 (9)
C13	0.8087 (5)	−0.5484 (6)	0.5934 (4)	0.0826 (15)
H13A	0.8393	−0.6523	0.6292	0.124*
H13B	0.8845	−0.5462	0.5515	0.124*
H13C	0.7179	−0.5094	0.5611	0.124*
C14	0.8965 (4)	−0.1662 (4)	0.6714 (3)	0.0451 (9)
C15	1.0684 (4)	−0.1085 (4)	0.6241 (3)	0.0448 (9)
C16	1.2096 (4)	−0.1293 (4)	0.5830 (2)	0.0462 (9)
C17	1.2653 (4)	−0.2022 (4)	0.5147 (3)	0.0517 (10)
H17	1.2092	−0.2343	0.4935	0.062*
C18	1.4018 (4)	−0.2279 (4)	0.4781 (3)	0.0541 (10)
C19	1.4847 (5)	−0.1822 (5)	0.5125 (3)	0.0601 (11)
H19	1.5771	−0.1994	0.4890	0.072*
C20	1.4338 (4)	−0.1120 (5)	0.5806 (3)	0.0593 (11)
H20	1.4923	−0.0842	0.6033	0.071*
C21	1.2969 (4)	−0.0835 (4)	0.6144 (3)	0.0484 (9)
C22	1.4585 (5)	−0.3024 (5)	0.4030 (3)	0.0714 (13)
H22A	1.4980	−0.4116	0.4271	0.107*
H22B	1.5352	−0.2805	0.3729	0.107*
H22C	1.3785	−0.2627	0.3611	0.107*
C23	1.1989 (4)	0.1327 (5)	0.6685 (3)	0.0501 (10)
C24	1.1406 (4)	0.1844 (4)	0.7505 (3)	0.0464 (9)
C25	1.1310 (4)	0.3182 (5)	0.7572 (3)	0.0574 (11)
H25	1.1609	0.3772	0.7103	0.069*
C26	1.0769 (5)	0.3626 (5)	0.8337 (3)	0.0663 (12)
H26	1.0705	0.4516	0.8399	0.080*
C27	1.0327 (4)	0.2743 (5)	0.9005 (3)	0.0572 (10)
H27	0.9951	0.3058	0.9520	0.069*
C28	1.0929 (4)	0.1006 (4)	0.8204 (2)	0.0456 (9)
H28	1.0971	0.0119	0.8153	0.055*
Cl1	0.79045 (12)	0.35642 (12)	1.11101 (8)	0.0620 (3)
Cu1	1.0000	0.0000	1.0000	0.0462 (2)
N1	0.7987 (3)	0.0684 (4)	0.9468 (2)	0.0507 (8)
N2	0.8640 (3)	−0.0468 (4)	0.6954 (2)	0.0511 (8)
N3	0.9776 (3)	−0.0077 (4)	0.6642 (2)	0.0509 (8)
N4	1.0405 (3)	0.1439 (3)	0.8958 (2)	0.0479 (8)
O1	1.0239 (3)	−0.2121 (3)	0.62421 (17)	0.0474 (6)
O2	0.7295 (3)	−0.1906 (3)	0.82628 (17)	0.0495 (6)
O3	0.5107 (3)	0.0069 (4)	0.7652 (2)	0.0818 (10)
O4	1.2472 (3)	−0.0193 (3)	0.68617 (17)	0.0483 (6)
O5	1.2029 (3)	0.2143 (3)	0.5975 (2)	0.0743 (9)
O6	0.6445 (4)	0.3796 (5)	1.1170 (4)	0.151 (2)
O7	0.8322 (6)	0.3522 (5)	1.1930 (3)	0.1442 (19)
O8	0.7933 (5)	0.4778 (4)	1.0446 (3)	0.1182 (16)
O9	0.8848 (3)	0.2139 (3)	1.0887 (2)	0.0764 (9)
C1	0.700 (4)	0.209 (5)	0.940 (3)	0.064 (8)	0.30 (4)
H1	0.7238	0.2716	0.9593	0.076*	0.30 (4)
C2	0.561 (3)	0.267 (4)	0.905 (4)	0.080 (11)	0.30 (4)
H2	0.4861	0.3633	0.9082	0.096*	0.30 (4)
C3	0.532 (3)	0.186 (2)	0.865 (3)	0.080 (11)	0.30 (4)
H3	0.4421	0.2303	0.8349	0.096*	0.30 (4)
C1'	0.6731 (19)	0.1792 (18)	0.9743 (13)	0.066 (4)	0.70 (4)
H1'	0.6848	0.2287	1.0109	0.079*	0.70 (4)
C2'	0.5315 (15)	0.2208 (18)	0.9507 (13)	0.082 (4)	0.70 (4)
H2'	0.4497	0.2977	0.9700	0.098*	0.70 (4)
C3'	0.5132 (11)	0.1480 (15)	0.8991 (11)	0.066 (4)	0.70 (4)
H3'	0.4182	0.1735	0.8829	0.079*	0.70 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C4	0.040 (2)	0.057 (2)	0.057 (3)	−0.0185 (19)	−0.0036 (18)	−0.024 (2)
C5	0.0377 (19)	0.053 (2)	0.051 (2)	−0.0215 (17)	0.0060 (17)	−0.0239 (19)
C6	0.041 (2)	0.076 (3)	0.062 (3)	−0.035 (2)	0.006 (2)	−0.024 (2)
C7	0.044 (2)	0.056 (2)	0.056 (2)	−0.0274 (18)	−0.0025 (19)	−0.022 (2)
C8	0.061 (3)	0.083 (3)	0.073 (3)	−0.050 (2)	0.016 (2)	−0.030 (3)
C9	0.070 (3)	0.076 (3)	0.085 (3)	−0.052 (3)	0.006 (3)	−0.033 (3)
C10	0.051 (2)	0.071 (3)	0.072 (3)	−0.034 (2)	0.002 (2)	−0.036 (2)
C11	0.045 (2)	0.069 (3)	0.058 (3)	−0.029 (2)	0.0022 (19)	−0.026 (2)
C12	0.0383 (19)	0.058 (2)	0.054 (2)	−0.0256 (18)	0.0030 (18)	−0.022 (2)
C13	0.080 (3)	0.085 (3)	0.110 (4)	−0.043 (3)	−0.002 (3)	−0.054 (3)
C14	0.040 (2)	0.057 (2)	0.046 (2)	−0.0269 (18)	0.0023 (17)	−0.0192 (19)
C15	0.043 (2)	0.050 (2)	0.048 (2)	−0.0269 (18)	−0.0035 (18)	−0.0127 (18)
C16	0.047 (2)	0.054 (2)	0.043 (2)	−0.0296 (18)	0.0072 (18)	−0.0145 (18)
C17	0.058 (2)	0.058 (2)	0.050 (2)	−0.035 (2)	0.005 (2)	−0.019 (2)
C18	0.053 (2)	0.056 (2)	0.053 (2)	−0.027 (2)	0.015 (2)	−0.018 (2)
C19	0.052 (2)	0.068 (3)	0.067 (3)	−0.034 (2)	0.021 (2)	−0.025 (2)
C20	0.051 (2)	0.074 (3)	0.068 (3)	−0.040 (2)	0.011 (2)	−0.024 (2)
C21	0.054 (2)	0.055 (2)	0.043 (2)	−0.0320 (19)	0.0068 (19)	−0.0144 (18)
C22	0.079 (3)	0.080 (3)	0.069 (3)	−0.045 (3)	0.022 (3)	−0.034 (3)
C23	0.0360 (19)	0.056 (2)	0.057 (3)	−0.0234 (18)	0.0069 (19)	−0.014 (2)
C24	0.0364 (19)	0.052 (2)	0.051 (2)	−0.0219 (17)	0.0005 (17)	−0.0136 (19)
C25	0.053 (2)	0.056 (2)	0.068 (3)	−0.033 (2)	0.000 (2)	−0.012 (2)
C26	0.073 (3)	0.049 (2)	0.084 (3)	−0.032 (2)	−0.008 (3)	−0.019 (2)
C27	0.063 (3)	0.060 (3)	0.058 (3)	−0.029 (2)	0.001 (2)	−0.030 (2)
C28	0.046 (2)	0.050 (2)	0.047 (2)	−0.0250 (18)	0.0055 (18)	−0.0192 (18)
Cl1	0.0616 (6)	0.0505 (6)	0.0743 (8)	−0.0240 (5)	−0.0045 (6)	−0.0206 (6)
Cu1	0.0479 (4)	0.0619 (4)	0.0419 (4)	−0.0314 (3)	0.0045 (3)	−0.0240 (3)
N1	0.0465 (18)	0.0529 (19)	0.061 (2)	−0.0241 (16)	0.0020 (16)	−0.0272 (17)
N2	0.0413 (17)	0.058 (2)	0.062 (2)	−0.0279 (15)	0.0086 (16)	−0.0243 (17)
N3	0.0443 (17)	0.057 (2)	0.061 (2)	−0.0294 (16)	0.0076 (16)	−0.0231 (17)
N4	0.0468 (18)	0.0517 (19)	0.053 (2)	−0.0255 (15)	0.0009 (15)	−0.0215 (16)
O1	0.0426 (14)	0.0593 (16)	0.0548 (16)	−0.0309 (13)	0.0088 (12)	−0.0263 (13)
O2	0.0446 (14)	0.0597 (17)	0.0532 (16)	−0.0282 (13)	0.0038 (12)	−0.0228 (14)
O3	0.0514 (17)	0.096 (2)	0.108 (3)	−0.0283 (17)	−0.0227 (18)	−0.044 (2)
O4	0.0534 (15)	0.0577 (16)	0.0467 (15)	−0.0355 (13)	0.0084 (13)	−0.0187 (13)
O5	0.081 (2)	0.0655 (19)	0.0581 (19)	−0.0322 (17)	0.0236 (17)	−0.0081 (16)
O6	0.067 (2)	0.154 (4)	0.272 (7)	−0.056 (3)	0.045 (3)	−0.126 (5)
O7	0.234 (6)	0.121 (4)	0.090 (3)	−0.091 (4)	−0.038 (3)	−0.020 (3)
O8	0.152 (4)	0.057 (2)	0.102 (3)	−0.029 (2)	0.037 (3)	−0.016 (2)
O9	0.0608 (18)	0.0482 (16)	0.114 (3)	−0.0201 (14)	0.0094 (18)	−0.0284 (18)
C1	0.051 (12)	0.076 (18)	0.09 (2)	−0.035 (11)	0.011 (14)	−0.050 (17)
C2	0.038 (11)	0.046 (12)	0.15 (3)	0.007 (8)	−0.011 (14)	−0.054 (17)
C3	0.028 (9)	0.10 (2)	0.09 (2)	−0.007 (11)	−0.008 (12)	−0.040 (15)
C1'	0.059 (8)	0.060 (6)	0.086 (10)	−0.021 (4)	0.003 (6)	−0.045 (7)
C2'	0.049 (5)	0.069 (7)	0.115 (10)	−0.007 (5)	0.005 (6)	−0.049 (7)
C3'	0.049 (5)	0.065 (5)	0.087 (8)	−0.021 (4)	0.001 (4)	−0.037 (6)

Geometric parameters (Å, º)

C4—C5	1.379 (5)	C22—H22A	0.9600
C4—C3	1.390 (10)	C22—H22B	0.9600
C4—C3'	1.394 (7)	C22—H22C	0.9600
C4—C6	1.482 (5)	C23—O5	1.184 (5)
C5—N1	1.334 (4)	C23—O4	1.350 (4)
C5—H5	0.9300	C23—C24	1.484 (5)
C6—O3	1.197 (5)	C24—C28	1.380 (5)
C6—O2	1.349 (5)	C24—C25	1.382 (5)
C7—C8	1.377 (5)	C25—C26	1.368 (6)
C7—C12	1.389 (5)	C25—H25	0.9300
C7—O2	1.402 (4)	C26—C27	1.360 (6)
C8—C9	1.393 (6)	C26—H26	0.9300
C8—H8	0.9300	C27—N4	1.344 (5)
C9—C10	1.374 (6)	C27—H27	0.9300
C9—H9	0.9300	C28—N4	1.345 (5)
C10—C11	1.374 (5)	C28—H28	0.9300
C10—C13	1.506 (6)	Cl1—O8	1.379 (4)
C11—C12	1.388 (5)	Cl1—O7	1.385 (4)
C11—H11	0.9300	Cl1—O6	1.402 (4)
C12—C14	1.458 (5)	Cl1—O9	1.442 (3)
C13—H13A	0.9600	Cu1—N4	2.006 (3)
C13—H13B	0.9600	Cu1—N4^i	2.006 (3)
C13—H13C	0.9600	Cu1—N1^i	2.038 (3)
C14—N2	1.280 (5)	Cu1—N1	2.038 (3)
C14—O1	1.363 (4)	Cu1—O9	2.676 (3)
C15—N3	1.289 (4)	N1—C1	1.29 (4)
C15—O1	1.364 (4)	N1—C1'	1.375 (17)
C15—C16	1.459 (5)	N2—N3	1.410 (4)
C16—C17	1.398 (5)	C1—C2	1.38 (4)
C16—C21	1.400 (5)	C1—H1	0.9300
C17—C18	1.382 (5)	C2—C3	1.342 (11)
C17—H17	0.9300	C2—H2	0.9300
C18—C19	1.386 (6)	C3—H3	0.9300
C18—C22	1.503 (6)	C1'—C2'	1.373 (19)
C19—C20	1.378 (6)	C1'—H1'	0.9300
C19—H19	0.9300	C2'—C3'	1.346 (9)
C20—C21	1.366 (5)	C2'—H2'	0.9300
C20—H20	0.9300	C3'—H3'	0.9300
C21—O4	1.395 (4)
C5—C4—C3	113.6 (12)	O5—C23—C24	124.3 (4)
C5—C4—C3'	118.3 (6)	O4—C23—C24	110.8 (3)
C5—C4—C6	122.3 (3)	C28—C24—C25	119.2 (4)
C3—C4—C6	119.7 (12)	C28—C24—C23	120.3 (3)
C3'—C4—C6	119.2 (6)	C25—C24—C23	120.5 (4)
N1—C5—C4	123.4 (3)	C26—C25—C24	119.1 (4)
N1—C5—H5	118.3	C26—C25—H25	120.4
C4—C5—H5	118.3	C24—C25—H25	120.4
O3—C6—O2	123.4 (4)	C27—C26—C25	118.8 (4)
O3—C6—C4	125.2 (4)	C27—C26—H26	120.6
O2—C6—C4	111.4 (3)	C25—C26—H26	120.6
C8—C7—C12	120.9 (4)	N4—C27—C26	123.4 (4)
C8—C7—O2	120.4 (4)	N4—C27—H27	118.3
C12—C7—O2	118.6 (3)	C26—C27—H27	118.3
C7—C8—C9	119.3 (4)	N4—C28—C24	121.7 (3)
C7—C8—H8	120.4	N4—C28—H28	119.2
C9—C8—H8	120.4	C24—C28—H28	119.2
C10—C9—C8	121.4 (4)	O8—Cl1—O7	109.8 (3)
C10—C9—H9	119.3	O8—Cl1—O6	108.5 (3)
C8—C9—H9	119.3	O7—Cl1—O6	108.2 (4)
C11—C10—C9	117.8 (4)	O8—Cl1—O9	110.4 (2)
C11—C10—C13	121.8 (4)	O7—Cl1—O9	111.5 (3)
C9—C10—C13	120.4 (4)	O6—Cl1—O9	108.3 (2)
C10—C11—C12	123.0 (4)	N4—Cu1—N4^i	180.000 (1)
C10—C11—H11	118.5	N4—Cu1—N1^i	87.39 (13)
C12—C11—H11	118.5	N4^i—Cu1—N1^i	92.61 (13)
C11—C12—C7	117.6 (3)	N4—Cu1—N1	92.61 (13)
C11—C12—C14	121.2 (3)	N4^i—Cu1—N1	87.39 (13)
C7—C12—C14	121.1 (3)	N1^i—Cu1—N1	180.0
C10—C13—H13A	109.5	N4—Cu1—O9	89.96 (12)
C10—C13—H13B	109.5	N4^i—Cu1—O9	90.04 (12)
H13A—C13—H13B	109.5	N1^i—Cu1—O9	86.95 (11)
C10—C13—H13C	109.5	N1—Cu1—O9	93.05 (11)
H13A—C13—H13C	109.5	C1—N1—C5	118.3 (16)
H13B—C13—H13C	109.5	C5—N1—C1'	115.8 (7)
N2—C14—O1	112.6 (3)	C1—N1—Cu1	115.5 (16)
N2—C14—C12	130.6 (3)	C5—N1—Cu1	124.0 (3)
O1—C14—C12	116.8 (3)	C1'—N1—Cu1	118.9 (7)
N3—C15—O1	112.8 (3)	C14—N2—N3	106.6 (3)
N3—C15—C16	129.8 (3)	C15—N3—N2	105.7 (3)
O1—C15—C16	117.4 (3)	C27—N4—C28	117.8 (3)
C17—C16—C21	118.1 (3)	C27—N4—Cu1	123.3 (3)
C17—C16—C15	121.3 (3)	C28—N4—Cu1	118.5 (2)
C21—C16—C15	120.5 (3)	C14—O1—C15	102.3 (3)
C18—C17—C16	121.5 (4)	C6—O2—C7	117.8 (3)
C18—C17—H17	119.2	C23—O4—C21	117.6 (3)
C16—C17—H17	119.2	Cl1—O9—Cu1	161.1 (2)
C17—C18—C19	118.0 (4)	N1—C1—C2	120 (3)
C17—C18—C22	121.0 (4)	N1—C1—H1	119.9
C19—C18—C22	121.0 (4)	C2—C1—H1	119.9
C20—C19—C18	121.9 (4)	C3—C2—C1	120 (2)
C20—C19—H19	119.1	C3—C2—H2	119.9
C18—C19—H19	119.1	C1—C2—H2	119.9
C21—C20—C19	119.5 (4)	C2—C3—C4	120.2 (19)
C21—C20—H20	120.3	C2—C3—H3	119.9
C19—C20—H20	120.3	C4—C3—H3	119.9
C20—C21—O4	120.0 (3)	C2'—C1'—N1	123.5 (12)
C20—C21—C16	121.0 (4)	C2'—C1'—H1'	118.2
O4—C21—C16	118.8 (3)	N1—C1'—H1'	118.2
C18—C22—H22A	109.5	C3'—C2'—C1'	118.7 (11)
C18—C22—H22B	109.5	C3'—C2'—H2'	120.6
H22A—C22—H22B	109.5	C1'—C2'—H2'	120.6
C18—C22—H22C	109.5	C2'—C3'—C4	119.8 (10)
H22A—C22—H22C	109.5	C2'—C3'—H3'	120.1
H22B—C22—H22C	109.5	C4—C3'—H3'	120.1
O5—C23—O4	124.9 (4)
C3—C4—C5—N1	20 (2)	N4^i—Cu1—N1—C1'	83.8 (10)
C3'—C4—C5—N1	−8.2 (11)	O9—Cu1—N1—C1'	−6.1 (10)
C6—C4—C5—N1	176.8 (4)	C12—C14—N2—N3	175.8 (4)
C5—C4—C6—O3	−157.1 (4)	C16—C15—N3—N2	−176.5 (4)
C3—C4—C6—O3	−2 (3)	C26—C27—N4—Cu1	171.9 (3)
C3'—C4—C6—O3	27.9 (11)	C24—C28—N4—Cu1	−171.8 (3)
C5—C4—C6—O2	24.0 (5)	N1^i—Cu1—N4—C27	−74.4 (3)
C3'—C4—C6—O2	−151.0 (9)	N1—Cu1—N4—C27	105.6 (3)
O2—C7—C8—C9	−173.7 (4)	O9—Cu1—N4—C27	12.6 (3)
C10—C11—C12—C14	176.0 (4)	N1^i—Cu1—N4—C28	98.5 (3)
O2—C7—C12—C11	174.4 (3)	N1—Cu1—N4—C28	−81.5 (3)
C8—C7—C12—C14	−177.4 (4)	O9—Cu1—N4—C28	−174.6 (3)
O2—C7—C12—C14	−2.1 (5)	C12—C14—O1—C15	−175.8 (3)
C11—C12—C14—N2	158.0 (4)	C16—C15—O1—C14	176.3 (3)
C7—C12—C14—N2	−25.6 (6)	O3—C6—O2—C7	13.1 (6)
C11—C12—C14—O1	−25.3 (5)	C4—C6—O2—C7	−167.9 (3)
C7—C12—C14—O1	151.1 (3)	C8—C7—O2—C6	−93.1 (4)
N3—C15—C16—C17	−155.3 (4)	C12—C7—O2—C6	91.7 (4)
O1—C15—C16—C17	27.2 (5)	O5—C23—O4—C21	−4.3 (6)
N3—C15—C16—C21	28.1 (6)	C24—C23—O4—C21	176.1 (3)
O1—C15—C16—C21	−149.4 (3)	C20—C21—O4—C23	76.7 (4)
C15—C16—C17—C18	−177.3 (4)	C16—C21—O4—C23	−108.5 (4)
C19—C20—C21—O4	176.9 (4)	O8—Cl1—O9—Cu1	−57.8 (6)
C19—C20—C21—C16	2.2 (6)	O6—Cl1—O9—Cu1	60.9 (6)
C15—C16—C21—C20	175.5 (4)	N4—Cu1—O9—Cl1	59.6 (6)
C17—C16—C21—O4	−176.0 (3)	N4^i—Cu1—O9—Cl1	−120.4 (6)
O5—C23—C24—C28	157.9 (4)	N1^i—Cu1—O9—Cl1	147.0 (6)
O4—C23—C24—C28	−22.4 (5)	N1—Cu1—O9—Cl1	−33.0 (6)
O5—C23—C24—C25	−21.0 (6)	C5—N1—C1—C2	16 (3)
O4—C23—C24—C25	158.6 (3)	C1'—N1—C1—C2	−76 (4)
C4—C5—N1—C1	−23 (2)	N1—C1—C2—C3	−10 (4)
C4—C5—N1—C1'	8.3 (11)	C1—C2—C3—C4	8 (4)
C4—C5—N1—Cu1	175.1 (3)	C5—C4—C3—C2	−13 (3)
N4—Cu1—N1—C1	−65 (2)	C3'—C4—C3—C2	94 (4)
N4^i—Cu1—N1—C1	115 (2)	C6—C4—C3—C2	−170 (2)
O9—Cu1—N1—C1	25 (2)	C1—N1—C1'—C2'	97 (5)
N4—Cu1—N1—C5	97.4 (3)	C5—N1—C1'—C2'	−4.8 (15)
N4^i—Cu1—N1—C5	−82.6 (3)	Cu1—N1—C1'—C2'	−172.3 (9)
O9—Cu1—N1—C5	−172.5 (3)	C5—C4—C3'—C2'	4.0 (14)
N4—Cu1—N1—C1'	−96.2 (10)	C3—C4—C3'—C2'	−82 (3)

Symmetry code: (i) −x+2, −y, −z+2.

(II) Diacetonitriledi-µ₃-iodido-di-µ₂-iodido-bis(4-methyl-{5-[5-methyl-2-(pyridin-4-ylcarbonyloxy)phenyl]-1,3,4-oxadiazol-2-yl}phenyl pyridine-4-carboxylate)tetracopper(I)

Crystal data

[Cu4I4(C2H3N)2(C28H20N4O5)2]	Z = 1
Mr = 1828.82	F(000) = 884
Triclinic, P1	Dx = 1.840 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.260 (2) Å	Cell parameters from 2048 reflections
b = 12.597 (3) Å	θ = 2.4–22.5°
c = 15.623 (4) Å	µ = 3.20 mm^−1
α = 96.709 (4)°	T = 298 K
β = 102.843 (4)°	Plate, yellow
γ = 108.464 (4)°	0.17 × 0.11 × 0.05 mm
V = 1650.6 (7) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	5713 independent reflections
Radiation source: fine-focus sealed tube	4168 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ϕ and ω scans	θmax = 25.0°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→10
Tmin = 0.612, Tmax = 0.856	k = −11→14
8387 measured reflections	l = −16→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.104	H-atom parameters constrained
S = 0.98	w = 1/[σ^2(Fo^2) + (0.0458P)^2] where P = (Fo^2 + 2Fc^2)/3
5713 reflections	(Δ/σ)max = 0.001
400 parameters	Δρmax = 0.82 e Å^−3
0 restraints	Δρmin = −0.44 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.9617 (8)	0.6776 (6)	0.0882 (5)	0.073 (2)
H1	0.9583	0.6166	0.0471	0.087*
C2	1.1085 (7)	0.7516 (6)	0.1438 (5)	0.078 (2)
H2	1.2007	0.7381	0.1412	0.094*
C3	1.1151 (6)	0.8435 (5)	0.2013 (4)	0.0435 (15)
C4	0.9796 (7)	0.8580 (6)	0.2062 (4)	0.0582 (18)
H4	0.9807	0.9197	0.2457	0.070*
C5	0.8375 (7)	0.7788 (6)	0.1509 (4)	0.064 (2)
H5	0.7438	0.7882	0.1557	0.077*
C6	1.2743 (6)	0.9201 (5)	0.2605 (4)	0.0441 (15)
C7	1.4026 (6)	1.0930 (5)	0.3665 (4)	0.0382 (14)
C8	1.5275 (7)	1.1676 (5)	0.3451 (4)	0.0442 (15)
H8	1.5261	1.1689	0.2855	0.053*
C9	1.6555 (7)	1.2409 (5)	0.4137 (4)	0.0475 (15)
H9	1.7414	1.2903	0.3996	0.057*
C10	1.6583 (6)	1.2422 (5)	0.5023 (4)	0.0439 (15)
C11	1.7980 (7)	1.3248 (5)	0.5778 (4)	0.0622 (19)
H11A	1.8506	1.2824	0.6118	0.093*
H11B	1.7603	1.3683	0.6162	0.093*
H11C	1.8709	1.3755	0.5527	0.093*
C12	1.5301 (6)	1.1664 (5)	0.5217 (4)	0.0404 (14)
H12	1.5307	1.1666	0.5813	0.049*
C13	1.4007 (6)	1.0902 (5)	0.4548 (4)	0.0387 (14)
C14	1.2701 (6)	1.0114 (5)	0.4782 (4)	0.0382 (14)
C15	1.1444 (6)	0.9331 (5)	0.5667 (4)	0.0378 (13)
C16	1.1188 (6)	0.9110 (5)	0.6532 (3)	0.0378 (13)
C17	1.2406 (7)	0.9653 (5)	0.7316 (4)	0.0468 (15)
H17	1.3358	1.0170	0.7287	0.056*
C18	1.2214 (8)	0.9433 (6)	0.8139 (4)	0.0563 (17)
C19	1.3567 (9)	0.9998 (8)	0.8978 (5)	0.099 (3)
H19A	1.3155	1.0043	0.9488	0.148*
H19B	1.4162	1.0754	0.8926	0.148*
H19C	1.4246	0.9556	0.9053	0.148*
C20	1.0785 (8)	0.8694 (6)	0.8174 (4)	0.064 (2)
H20	1.0638	0.8554	0.8725	0.077*
C21	0.9559 (7)	0.8154 (5)	0.7402 (4)	0.0552 (18)
H21	0.8596	0.7657	0.7435	0.066*
C22	0.9775 (6)	0.8356 (5)	0.6590 (4)	0.0398 (14)
C23	0.8430 (7)	0.6764 (5)	0.5428 (4)	0.0487 (16)
C24	0.7189 (7)	0.6311 (5)	0.4547 (4)	0.0427 (14)
C25	0.6337 (8)	0.5165 (6)	0.4302 (4)	0.066 (2)
H25	0.6510	0.4679	0.4685	0.080*
C26	0.5222 (9)	0.4739 (6)	0.3484 (4)	0.072 (2)
H26	0.4646	0.3958	0.3328	0.087*
C27	0.5750 (7)	0.6496 (5)	0.3157 (4)	0.0566 (18)
H27	0.5554	0.6968	0.2766	0.068*
C28	0.6887 (7)	0.6984 (6)	0.3972 (4)	0.0575 (18)
H28	0.7437	0.7768	0.4121	0.069*
C29	−0.0016 (9)	0.4369 (7)	0.1978 (5)	0.070 (2)
C30	−0.1524 (9)	0.4270 (9)	0.2189 (6)	0.124 (4)
H30A	−0.1345	0.4428	0.2828	0.185*
H30B	−0.2273	0.3510	0.1943	0.185*
H30C	−0.1935	0.4808	0.1935	0.185*
Cu1	0.61992 (8)	0.59952 (7)	−0.00532 (5)	0.0504 (2)
Cu2	0.32599 (9)	0.46142 (7)	0.16747 (5)	0.0577 (2)
I1	0.63518 (5)	0.73364 (4)	−0.12381 (3)	0.05890 (16)
I2	0.37871 (5)	0.60721 (3)	0.05724 (3)	0.04790 (14)
N1	0.8283 (5)	0.6913 (4)	0.0923 (3)	0.0485 (13)
N2	1.1401 (5)	0.9364 (4)	0.4280 (3)	0.0483 (13)
N3	1.0559 (5)	0.8835 (4)	0.4861 (3)	0.0503 (13)
N4	0.4931 (6)	0.5385 (4)	0.2911 (3)	0.0515 (14)
N5	0.1113 (7)	0.4465 (5)	0.1829 (4)	0.0656 (16)
O1	1.2817 (4)	1.0159 (3)	0.5673 (2)	0.0382 (9)
O2	0.9247 (6)	0.6263 (4)	0.5744 (3)	0.0799 (16)
O3	0.8535 (4)	0.7809 (3)	0.5805 (2)	0.0404 (9)
O4	1.2693 (4)	1.0209 (3)	0.2971 (2)	0.0442 (10)
O5	1.3878 (5)	0.8942 (4)	0.2758 (3)	0.0699 (14)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.051 (4)	0.079 (5)	0.070 (5)	0.024 (4)	0.003 (4)	−0.031 (4)
C2	0.029 (3)	0.086 (5)	0.093 (5)	0.023 (3)	−0.007 (3)	−0.041 (5)
C3	0.032 (3)	0.053 (4)	0.038 (3)	0.014 (3)	0.002 (3)	0.001 (3)
C4	0.043 (4)	0.062 (4)	0.056 (4)	0.019 (3)	0.002 (3)	−0.020 (3)
C5	0.033 (3)	0.082 (5)	0.061 (4)	0.015 (3)	0.005 (3)	−0.021 (4)
C6	0.027 (3)	0.055 (4)	0.045 (4)	0.013 (3)	0.006 (3)	0.000 (3)
C7	0.036 (3)	0.034 (3)	0.040 (3)	0.013 (3)	0.000 (3)	0.009 (3)
C8	0.044 (3)	0.038 (3)	0.047 (4)	0.013 (3)	0.009 (3)	0.008 (3)
C9	0.039 (3)	0.040 (4)	0.062 (4)	0.009 (3)	0.018 (3)	0.011 (3)
C10	0.031 (3)	0.033 (3)	0.058 (4)	0.008 (3)	0.005 (3)	−0.002 (3)
C11	0.053 (4)	0.046 (4)	0.068 (4)	0.003 (3)	0.010 (3)	−0.008 (4)
C12	0.040 (3)	0.036 (3)	0.038 (3)	0.010 (3)	0.005 (3)	0.000 (3)
C13	0.034 (3)	0.035 (3)	0.044 (3)	0.012 (3)	0.005 (3)	0.005 (3)
C14	0.035 (3)	0.037 (3)	0.038 (3)	0.010 (3)	0.006 (3)	0.004 (3)
C15	0.031 (3)	0.035 (3)	0.043 (3)	0.011 (3)	0.004 (3)	0.003 (3)
C16	0.038 (3)	0.033 (3)	0.037 (3)	0.010 (3)	0.007 (3)	0.001 (3)
C17	0.037 (3)	0.054 (4)	0.042 (3)	0.013 (3)	0.006 (3)	0.002 (3)
C18	0.055 (4)	0.063 (4)	0.039 (4)	0.016 (3)	0.003 (3)	0.000 (3)
C19	0.082 (6)	0.129 (8)	0.051 (5)	0.019 (5)	−0.014 (4)	0.005 (5)
C20	0.077 (5)	0.074 (5)	0.037 (4)	0.021 (4)	0.015 (3)	0.015 (4)
C21	0.052 (4)	0.058 (4)	0.043 (4)	0.003 (3)	0.012 (3)	0.010 (3)
C22	0.038 (3)	0.042 (4)	0.036 (3)	0.014 (3)	0.006 (3)	0.002 (3)
C23	0.047 (4)	0.042 (4)	0.046 (4)	0.010 (3)	0.004 (3)	0.005 (3)
C24	0.044 (3)	0.037 (3)	0.041 (3)	0.015 (3)	0.005 (3)	−0.003 (3)
C25	0.078 (5)	0.039 (4)	0.059 (4)	0.006 (4)	−0.004 (4)	0.009 (3)
C26	0.087 (5)	0.045 (4)	0.049 (4)	−0.005 (4)	−0.002 (4)	−0.004 (4)
C27	0.058 (4)	0.047 (4)	0.050 (4)	0.012 (3)	−0.003 (3)	0.008 (3)
C28	0.057 (4)	0.047 (4)	0.052 (4)	0.009 (3)	0.000 (3)	0.003 (3)
C29	0.055 (5)	0.089 (6)	0.068 (5)	0.018 (4)	0.023 (4)	0.025 (4)
C30	0.061 (5)	0.207 (12)	0.120 (8)	0.048 (6)	0.047 (5)	0.056 (8)
Cu1	0.0402 (4)	0.0557 (5)	0.0432 (4)	0.0094 (4)	0.0046 (3)	−0.0016 (4)
Cu2	0.0468 (5)	0.0644 (6)	0.0478 (5)	0.0077 (4)	0.0079 (4)	0.0015 (4)
I1	0.0690 (3)	0.0581 (3)	0.0483 (3)	0.0177 (2)	0.0198 (2)	0.0121 (2)
I2	0.0453 (2)	0.0494 (3)	0.0498 (3)	0.01617 (19)	0.01843 (18)	0.0049 (2)
N1	0.035 (3)	0.058 (3)	0.042 (3)	0.014 (2)	0.002 (2)	−0.004 (3)
N2	0.039 (3)	0.052 (3)	0.036 (3)	−0.001 (2)	0.005 (2)	0.005 (2)
N3	0.033 (3)	0.057 (3)	0.042 (3)	0.001 (2)	0.000 (2)	0.001 (3)
N4	0.051 (3)	0.046 (3)	0.040 (3)	0.004 (3)	0.001 (2)	0.003 (3)
N5	0.049 (4)	0.081 (4)	0.067 (4)	0.017 (3)	0.026 (3)	0.014 (3)
O1	0.031 (2)	0.034 (2)	0.034 (2)	0.0001 (17)	−0.0004 (16)	−0.0024 (17)
O2	0.085 (4)	0.057 (3)	0.072 (3)	0.030 (3)	−0.024 (3)	−0.010 (3)
O3	0.035 (2)	0.039 (2)	0.037 (2)	0.0073 (18)	0.0021 (17)	0.0012 (19)
O4	0.035 (2)	0.049 (3)	0.040 (2)	0.0107 (19)	0.0014 (17)	0.004 (2)
O5	0.038 (3)	0.069 (3)	0.084 (3)	0.021 (2)	−0.004 (2)	−0.019 (3)

Geometric parameters (Å, º)

C1—N1	1.315 (8)	C19—H19B	0.9600
C1—C2	1.398 (8)	C19—H19C	0.9600
C1—H1	0.9300	C20—C21	1.385 (8)
C2—C3	1.356 (8)	C20—H20	0.9300
C2—H2	0.9300	C21—C22	1.368 (8)
C3—C4	1.341 (8)	C21—H21	0.9300
C3—C6	1.499 (7)	C22—O3	1.404 (6)
C4—C5	1.390 (8)	C23—O2	1.193 (7)
C4—H4	0.9300	C23—O3	1.342 (7)
C5—N1	1.316 (8)	C23—C24	1.496 (8)
C5—H5	0.9300	C24—C28	1.348 (8)
C6—O5	1.179 (7)	C24—C25	1.367 (8)
C6—O4	1.348 (7)	C25—C26	1.374 (8)
C7—C8	1.375 (7)	C25—H25	0.9300
C7—C13	1.389 (7)	C26—N4	1.319 (8)
C7—O4	1.410 (6)	C26—H26	0.9300
C8—C9	1.384 (8)	C27—N4	1.324 (7)
C8—H8	0.9300	C27—C28	1.385 (8)
C9—C10	1.378 (8)	C27—H27	0.9300
C9—H9	0.9300	C28—H28	0.9300
C10—C12	1.386 (7)	C29—N5	1.095 (8)
C10—C11	1.525 (7)	C29—C30	1.476 (11)
C11—H11A	0.9600	C30—H30A	0.9600
C11—H11B	0.9600	C30—H30B	0.9600
C11—H11C	0.9600	C30—H30C	0.9600
C12—C13	1.389 (7)	Cu1—N1	2.062 (4)
C12—H12	0.9300	Cu1—I2^i	2.6406 (11)
C13—C14	1.450 (7)	Cu1—I1	2.6452 (10)
C14—N2	1.282 (6)	Cu1—I2	2.6532 (10)
C14—O1	1.365 (6)	Cu1—Cu2^i	2.7589 (13)
C15—N3	1.297 (6)	Cu1—Cu1^i	2.8252 (16)
C15—O1	1.363 (6)	Cu2—N5	2.007 (6)
C15—C16	1.465 (7)	Cu2—N4	2.085 (5)
C16—C22	1.382 (7)	Cu2—I1^i	2.6287 (12)
C16—C17	1.394 (7)	Cu2—I2	2.6688 (10)
C17—C18	1.384 (8)	Cu2—Cu1^i	2.7589 (13)
C17—H17	0.9300	I1—Cu2^i	2.6287 (12)
C18—C20	1.372 (9)	I2—Cu1^i	2.6406 (11)
C18—C19	1.510 (8)	N2—N3	1.415 (6)
C19—H19A	0.9600
N1—C1—C2	122.1 (6)	C21—C22—C16	120.8 (5)
N1—C1—H1	118.9	C21—C22—O3	119.7 (5)
C2—C1—H1	118.9	C16—C22—O3	119.4 (5)
C3—C2—C1	119.3 (6)	O2—C23—O3	124.3 (5)
C3—C2—H2	120.3	O2—C23—C24	123.9 (6)
C1—C2—H2	120.3	O3—C23—C24	111.8 (6)
C4—C3—C2	118.9 (5)	C28—C24—C25	118.2 (5)
C4—C3—C6	123.2 (6)	C28—C24—C23	122.8 (5)
C2—C3—C6	117.8 (6)	C25—C24—C23	119.0 (6)
C3—C4—C5	118.6 (6)	C24—C25—C26	119.4 (6)
C3—C4—H4	120.7	C24—C25—H25	120.3
C5—C4—H4	120.7	C26—C25—H25	120.3
N1—C5—C4	123.6 (6)	N4—C26—C25	123.0 (6)
N1—C5—H5	118.2	N4—C26—H26	118.5
C4—C5—H5	118.2	C25—C26—H26	118.5
O5—C6—O4	124.4 (5)	N4—C27—C28	122.9 (6)
O5—C6—C3	124.5 (6)	N4—C27—H27	118.6
O4—C6—C3	111.1 (5)	C28—C27—H27	118.6
C8—C7—C13	121.8 (5)	C24—C28—C27	119.4 (6)
C8—C7—O4	119.3 (5)	C24—C28—H28	120.3
C13—C7—O4	118.9 (5)	C27—C28—H28	120.3
C7—C8—C9	118.9 (6)	N5—C29—C30	178.6 (10)
C7—C8—H8	120.5	C29—C30—H30A	109.5
C9—C8—H8	120.5	C29—C30—H30B	109.5
C10—C9—C8	121.4 (6)	H30A—C30—H30B	109.5
C10—C9—H9	119.3	C29—C30—H30C	109.5
C8—C9—H9	119.3	H30A—C30—H30C	109.5
C9—C10—C12	118.3 (5)	H30B—C30—H30C	109.5
C9—C10—C11	121.3 (5)	N1—Cu1—I2^i	108.43 (15)
C12—C10—C11	120.4 (6)	N1—Cu1—I1	100.39 (14)
C10—C11—H11A	109.5	I2^i—Cu1—I1	116.89 (3)
C10—C11—H11B	109.5	N1—Cu1—I2	108.77 (15)
H11A—C11—H11B	109.5	I2^i—Cu1—I2	115.49 (3)
C10—C11—H11C	109.5	I1—Cu1—I2	105.64 (3)
H11A—C11—H11C	109.5	N1—Cu1—Cu2^i	111.69 (15)
H11B—C11—H11C	109.5	I2^i—Cu1—Cu2^i	59.19 (3)
C10—C12—C13	122.0 (5)	I1—Cu1—Cu2^i	58.17 (3)
C10—C12—H12	119.0	I2—Cu1—Cu2^i	138.45 (3)
C13—C12—H12	119.0	N1—Cu1—Cu1^i	126.70 (15)
C7—C13—C12	117.6 (5)	I2^i—Cu1—Cu1^i	57.96 (3)
C7—C13—C14	122.2 (5)	I1—Cu1—Cu1^i	132.53 (4)
C12—C13—C14	120.2 (5)	I2—Cu1—Cu1^i	57.53 (3)
N2—C14—O1	112.6 (5)	Cu2^i—Cu1—Cu1^i	102.95 (4)
N2—C14—C13	130.3 (5)	N5—Cu2—N4	108.2 (2)
O1—C14—C13	117.1 (4)	N5—Cu2—I1^i	114.74 (18)
N3—C15—O1	112.3 (5)	N4—Cu2—I1^i	104.17 (16)
N3—C15—C16	129.8 (5)	N5—Cu2—I2	105.38 (17)
O1—C15—C16	117.9 (4)	N4—Cu2—I2	107.49 (15)
C22—C16—C17	118.8 (5)	I1^i—Cu2—I2	116.48 (4)
C22—C16—C15	121.6 (5)	N5—Cu2—Cu1^i	123.96 (16)
C17—C16—C15	119.6 (5)	N4—Cu2—Cu1^i	127.77 (15)
C18—C17—C16	120.8 (6)	I1^i—Cu2—Cu1^i	58.75 (3)
C18—C17—H17	119.6	I2—Cu2—Cu1^i	58.19 (3)
C16—C17—H17	119.6	Cu2^i—I1—Cu1	63.08 (3)
C20—C18—C17	118.8 (5)	Cu1^i—I2—Cu1	64.51 (3)
C20—C18—C19	121.2 (6)	Cu1^i—I2—Cu2	62.61 (3)
C17—C18—C19	119.9 (6)	Cu1—I2—Cu2	110.35 (3)
C18—C19—H19A	109.5	C1—N1—C5	117.3 (5)
C18—C19—H19B	109.5	C1—N1—Cu1	120.8 (4)
H19A—C19—H19B	109.5	C5—N1—Cu1	120.8 (4)
C18—C19—H19C	109.5	C14—N2—N3	106.5 (4)
H19A—C19—H19C	109.5	C15—N3—N2	105.8 (4)
H19B—C19—H19C	109.5	C26—N4—C27	117.2 (5)
C18—C20—C21	121.2 (6)	C26—N4—Cu2	118.9 (4)
C18—C20—H20	119.4	C27—N4—Cu2	123.9 (4)
C21—C20—H20	119.4	C29—N5—Cu2	174.4 (6)
C22—C21—C20	119.5 (6)	C15—O1—C14	102.8 (4)
C22—C21—H21	120.2	C23—O3—C22	116.1 (5)
C20—C21—H21	120.2	C6—O4—C7	117.1 (4)
N1—C1—C2—C3	−2.7 (12)	N5—Cu2—I2—Cu1	−165.57 (17)
C1—C2—C3—C4	2.9 (11)	N4—Cu2—I2—Cu1	79.24 (16)
C6—C3—C4—C5	−177.1 (6)	I1^i—Cu2—I2—Cu1	−37.11 (4)
C4—C3—C6—O5	158.3 (7)	Cu1^i—Cu2—I2—Cu1	−44.83 (3)
C2—C3—C6—O5	−18.0 (10)	C2—C1—N1—Cu1	168.6 (6)
C4—C3—C6—O4	−19.1 (8)	C4—C5—N1—Cu1	−166.4 (5)
C2—C3—C6—O4	164.7 (6)	I2^i—Cu1—N1—C1	36.0 (6)
O4—C7—C8—C9	177.8 (5)	I1—Cu1—N1—C1	−87.1 (5)
O4—C7—C13—C12	−176.7 (5)	I2—Cu1—N1—C1	162.3 (5)
O4—C7—C13—C14	3.4 (8)	Cu2^i—Cu1—N1—C1	−27.3 (6)
N3—C15—C16—C22	−7.1 (10)	Cu1^i—Cu1—N1—C1	99.3 (5)
O1—C15—C16—C22	174.4 (5)	I2^i—Cu1—N1—C5	−156.1 (5)
N3—C15—C16—C17	171.5 (6)	I1—Cu1—N1—C5	80.9 (5)
O1—C15—C16—C17	−6.9 (8)	I2—Cu1—N1—C5	−29.7 (5)
C15—C16—C17—C18	−177.9 (6)	Cu2^i—Cu1—N1—C5	140.6 (5)
C16—C17—C18—C19	177.8 (6)	Cu1^i—Cu1—N1—C5	−92.7 (5)
O2—C23—C24—C28	−143.0 (7)	C16—C15—N3—N2	−178.2 (6)
O3—C23—C24—C28	35.5 (8)	C25—C26—N4—Cu2	177.9 (6)
O2—C23—C24—C25	36.0 (10)	N5—Cu2—N4—C26	85.9 (6)
O3—C23—C24—C25	−145.6 (6)	I1^i—Cu2—N4—C26	−36.6 (6)
N1—Cu1—I1—Cu2^i	109.17 (16)	I2—Cu2—N4—C26	−160.8 (5)
I2^i—Cu1—I1—Cu2^i	−7.79 (3)	Cu1^i—Cu2—N4—C26	−97.9 (5)
I2—Cu1—I1—Cu2^i	−137.81 (3)	N5—Cu2—N4—C27	−95.2 (6)
Cu1^i—Cu1—I1—Cu2^i	−77.79 (7)	I1^i—Cu2—N4—C27	142.3 (5)
N1—Cu1—I2—Cu1^i	−122.13 (16)	I2—Cu2—N4—C27	18.1 (6)
I1—Cu1—I2—Cu1^i	130.83 (4)	Cu1^i—Cu2—N4—C27	81.0 (6)
Cu2^i—Cu1—I2—Cu1^i	71.49 (5)	C16—C15—O1—C14	177.9 (5)
N1—Cu1—I2—Cu2	−78.22 (16)	O2—C23—O3—C22	4.7 (9)
I2^i—Cu1—I2—Cu2	43.91 (4)	C24—C23—O3—C22	−173.7 (5)
I1—Cu1—I2—Cu2	174.74 (2)	C21—C22—O3—C23	−86.2 (7)
Cu2^i—Cu1—I2—Cu2	115.40 (5)	C16—C22—O3—C23	95.1 (6)
Cu1^i—Cu1—I2—Cu2	43.91 (4)	O5—C6—O4—C7	−8.5 (9)
N5—Cu2—I2—Cu1^i	−120.74 (17)	C3—C6—O4—C7	168.9 (4)
N4—Cu2—I2—Cu1^i	124.07 (16)	C8—C7—O4—C6	86.8 (7)
I1^i—Cu2—I2—Cu1^i	7.72 (3)	C13—C7—O4—C6	−96.1 (6)

Symmetry code: (i) −x+1, −y+1, −z.